CN114471506B - Carrier material and preparation method thereof, catalyst and application - Google Patents
Carrier material and preparation method thereof, catalyst and application Download PDFInfo
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- CN114471506B CN114471506B CN202011166321.0A CN202011166321A CN114471506B CN 114471506 B CN114471506 B CN 114471506B CN 202011166321 A CN202011166321 A CN 202011166321A CN 114471506 B CN114471506 B CN 114471506B
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- carrier
- preparing
- catalyst
- support material
- material according
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000012876 carrier material Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 43
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 230000006911 nucleation Effects 0.000 claims description 23
- 238000010899 nucleation Methods 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000005096 rolling process Methods 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000009489 vacuum treatment Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- -1 VIB metals Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003921 oil Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910018104 Ni-P Inorganic materials 0.000 description 8
- 229910018536 Ni—P Inorganic materials 0.000 description 8
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 8
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a carrier material, a preparation method thereof, a catalyst and application, wherein the carrier material is hollow carbon-containing alumina, and the preparation method comprises the following steps: (1) preparing a carrier mother ball; (2) preparing a carrier precursor; (3) preparing a carrier. Introducing active metal components into the prepared carrier material, and further drying and roasting to obtain the hydrogenation catalyst. The carrier material provided by the invention is carbon-containing alumina with a hollow structure, and the catalyst prepared by taking the carrier material as a carrier can greatly shorten the diffusion path of reactants in the catalytic material, improve the pore channel utilization rate of the catalytic material, reduce the use amount of active metal of the catalyst, improve the utilization rate of the active metal, and have proper actions between the carrier and the active metal, so that the obtained catalyst has high impurity removal activity, and is particularly suitable for the field of heavy oil and residual oil hydrogenation catalysis.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a catalytic material, and a preparation method and application thereof.
Background
With the rapid development of the economic society in China, the environmental pollution is more serious, the awareness of people on environmental protection is gradually enhanced, the national environmental protection regulations are increasingly strict, and higher requirements are put on the quality of fuel oil. This has prompted refineries to develop cleaner production processes and produce cleaner quality clean fuels. Meanwhile, along with gradual decrease of light crude oil supply and gradual increase of the proportion of heavy high-sulfur crude oil, the processing of poor crude oil becomes an urgent problem facing a refinery and is a key for influencing economic benefit of the whole plant. The boiling bed hydrogenation technology can effectively process inferior crude oil, reduce the impurity content in the raw oil, not only can provide high-quality raw materials for a oiling device, but also can directly produce high-quality fuel oil, and the catalyst plays a key role in the technology, so that the development of the high-activity residual oil hydrogenation catalyst is important, wherein the development of a carrier material is key.
Patent CN104096584B discloses a residuum hydrogenation catalyst and a preparation method thereof. The catalyst takes a mixed and kneaded body of alumina and active carbon as a carrier, and the active component is Ni 2 P、MoO 3 And/or WO 3 And/or CoO and/or NiO. A small amount of activated carbon is introduced into the alumina, thereby reducing Ni 2 The reaction with alumina in the process of generating the P active component improves the dispersivity and fully plays the role of Ni 2 The high activity of P and the carrier advantage of the alumina-activated carbon mixed body, thereby improving the impurity removing capability of the catalyst. However, due to the introduction of the active carbon in the catalyst carrier, the pore diameter of the carrier becomes smaller, impurities in the raw oil are removed outside the catalyst, the utilization rate of active metals in the catalyst is lower, uneven distribution of the impurity metals on the catalyst can be caused in long-period operation of the catalyst, pore canal blockage is caused, and the catalyst is deactivated.
Patent CN109833890a discloses a residuum hydrogenation catalyst and preparation thereof. The preparation method of the catalyst comprises the following steps: organic solvent spray-dipping residual oil hydrodemetallization catalyst carrier containing span surfactantAnd then drying; then the dried carrier is impregnated with an active metal solution containing polyacrylate, and then the catalyst is prepared by drying and roasting. The residual oil hydrogenation catalyst prepared by the method has the advantages of high active metal utilization rate, high metal dispersity, high activity and the like. But the catalyst adopts Al 2 O 3 The carrier has stronger interaction with active components, which leads to incomplete vulcanization of active metals and limits the further improvement of the catalytic reaction performance in the residual oil hydrogenation reaction.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a carrier material, a preparation method, a catalyst and application thereof, wherein the carrier material is carbon-containing alumina with a hollow structure, and the catalyst prepared by taking the carrier material as a carrier can greatly shorten the diffusion path of reactants in the catalytic material, improve the channel utilization rate of the catalytic material, reduce the use amount of active metal of the catalyst, improve the utilization rate of the active metal, and has proper action between the carrier and the active metal, so that the obtained catalyst has high impurity removal activity and is particularly suitable for the field of heavy oil and residual oil hydrogenation catalysis.
The first aspect of the present invention provides a method for preparing a carrier material, the method comprising the following steps:
(1) Preparing a carrier mother ball: the nucleation material is contacted with pseudo-boehmite powder carried by carrier gas in the form of fog drops for treatment;
(2) Preparing a carrier precursor: the carrier mother ball obtained in the step (1) is contacted with pseudo-boehmite powder and a high-molecular polymer solution for treatment;
(3) Preparing a carrier: and (3) treating the carrier precursor obtained in the step (2) under vacuum conditions, and further carrying out high-temperature heat treatment under inert atmosphere after the treatment is finished.
In the preparation method of the carrier material, in the step (1), the nucleation material is a hydrocarbon-containing material, the initial boiling point of the hydrocarbon-containing material is greater than 350 ℃, preferably greater than 450 ℃, and the nucleation material can be one or more selected from atmospheric residuum, vacuum residuum, asphalt and wax oil.
In the preparation method of the carrier material, the carrier gas in the step (1) is one or more of nitrogen and inert gas, preferably nitrogen; the carrier gas is preferably heated to a temperature of 50 to 100 ℃.
In the above-mentioned method for producing a carrier material, the treatment in the step (1) may be performed in a spray-drying apparatus, a spray-dipping apparatus or the like, and preferably a spray-drying apparatus is used. The specific model of the spray drying apparatus is not particularly limited, and any spray drying apparatus commonly used in the art may be used. The treatment process specifically comprises the following steps: firstly, heating the nucleation material to a liquid state, wherein the heating temperature is 100-200 ℃, then spraying the nucleation material into the spray drying device through a first feeding hole to form small fog drops, and spraying pseudo-boehmite powder from a second feeding hole through carrier gas, wherein the nucleation material sprayed from the first feeding hole and the pseudo-boehmite powder entering the second feeding hole are in reverse contact. The carrier gas temperature is 50-100 ℃, the treated material is further cooled to obtain carrier mother balls, the cooling temperature is 20-40 ℃, and the cooling time is 1-4 h. The particle size of the carrier matrix is controlled to be 0.2-0.8 mm.
In the preparation method of the carrier material, the pseudo-boehmite powder in the step (1) and the pseudo-boehmite powder in the step (2) can be the same pseudo-boehmite powder or different pseudo-boehmite powders. The pseudo-boehmite powder in the step (1) and the step (2) can be prepared according to methods disclosed in the prior literature or patents to obtain the pseudo-boehmite powder, such as a precipitation method, an aluminum alkoxide hydrolysis method, an inorganic salt sol-gel method, a hydrothermal method, a vapor deposition method and the like, or can also be prepared by adopting commercial products.
In the preparation method of the carrier material, in the step (2), the contact treatment of the carrier mother balls obtained in the step (1), the pseudo-boehmite powder and the solution can be realized by adopting a rolling ball method and a spray dipping method, and the further specific process is that the carrier mother balls are uniformly added with the pseudo-boehmite powder and the solution in the rolling process, and preferably, the high polymer solution and the pseudo-boehmite powder are sequentially and alternately added to obtain the carrier precursor. The treatment in step (2) may be carried out in a ball machine, a shot blasting machine or the like, preferably a ball machine.
In the preparation method of the carrier material, the high polymer solution in the step (2) can be one or more of starch, sesbania powder and methylcellulose, and is preferably starch; the high polymer solution is obtained by uniformly mixing a high polymer with water, preferably at 40-60 ℃. The addition amount of the high molecular polymer is 1-10wt% of the dry basis weight of the pseudo-boehmite powder in the step (2).
In the preparation method of the carrier material, the vacuum treatment conditions in the step (3) are as follows: the relative vacuum degree is-0.2 to 0MPa, preferably-0.1 MPa; the treatment temperature is 60-120 ℃, preferably comprises two steps, wherein the first step is 60-90 ℃, the treatment time is 3-8 h, the second step is 90-120 ℃, and the treatment time is 5-15 min.
In the preparation method of the carrier material, the high-temperature heat treatment in the step (3) comprises two sections, wherein the first section heat treatment temperature is 200-400 ℃ and the heat treatment time is 0.5-3 h; the second stage heat treatment temperature is 500-900 ℃, preferably 600-800 ℃; the heat treatment time is 1-5 h. The inert atmosphere in step (3) may be nitrogen and/or an inert gas, preferably nitrogen, and the inert gas is one or more of helium, neon, argon, krypton, and xenon.
In the preparation method of the carrier material, the particle size of the carrier in the step (3) is 0.8-2.0 mm.
The second aspect of the invention provides a carrier material obtained by the preparation method, wherein the carrier material is hollow carbon-containing alumina, and the specific surface area of the carrier material is 180-320 m 2 Per g, pore volume is 0.60-1.0 mL/g, and water absorption rate is 1.0-1.20 mL/g.
The third aspect of the invention provides a preparation method of a hydrogenation catalyst, wherein the preparation method comprises the steps of introducing an active metal component onto a carrier material prepared by the method, and further drying and roasting to obtain the hydrogenation catalyst.
In the preparation method of the hydrogenation catalyst, the manner of introducing the active metal component is not limited, and a person skilled in the art can adopt any one of the methods existing in the art according to actual needs, for example, any one of kneading, coprecipitation, impregnation and the like, preferably adopts impregnation, and can adopt isovolumetric impregnation, supersaturation impregnation, stepwise impregnation and co-impregnation. The specific impregnation method is a requisite basic skill of the person skilled in the art, and the final catalyst can be prepared by impregnating the support with the solution of the hydrogenation-active metal component, followed by drying and calcination. Methods of catalyst preparation are well known to the skilled artisan. The impregnating solution is generally prepared by using a group VIB and/or group VIII metal-containing compound, which may be one or more of a molybdenum-containing compound and a tungsten-containing compound, and which may be one or more of a nickel-containing compound and a cobalt-containing compound. The molybdenum-containing compound may be molybdenum oxide and/or ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate and/or nickel nitrate; the cobalt-containing compound is basic cobalt carbonate and/or cobalt nitrate. The concentration of the solution can be adjusted by the amount of each compound to prepare a catalyst having a specified active ingredient content, and the preparation method of the solution is well known to those skilled in the art. And adding the catalyst carrier into excessive water solution containing active metal component for soaking, evaporating the solution after soaking, and further drying and roasting to obtain the catalyst material. The drying conditions are typically: the drying temperature is 60-200 ℃, preferably 90-160 ℃, and the drying time is 0.5-20 h, preferably 1-6 h; the roasting conditions are as follows: the roasting is carried out under nitrogen or inert atmosphere, the roasting temperature is 300-700 ℃, preferably 300-500 ℃, and the roasting time is 0.5-20 h, preferably 1-6 h.
In the preparation method of the hydrogenation catalyst, one or more of other metals such as Fe, zr, ti, B, la, ce can be introduced.
The fourth aspect of the invention provides a hydrogenation catalyst obtained by the preparation method, which comprises a hydrogenation active metal component and a carrier, wherein the hydrogenation active metal component is one or more of VIB group metal and/or VIII group metal, and the carrier is hollow carbon-containing alumina.
In the hydrogenation catalyst, the concentration of the hydrogenation active metal-containing compound in the solution and the dosage of the solution are calculated by oxide and based on the catalyst, so that the content of the metal component of the VIB group in the final catalyst is 5-20wt%; the content of the metal component of the VIII group is 1 to 6 weight percent.
In the hydrogenation catalyst, the VIB group metal is Mo and/or W, and the VIII group metal is Ni and/or Co.
In the above hydrogenation catalyst, the hydrogenation metal component is more preferably Mo and Ni.
In the hydrogenation catalyst described above, the catalyst support may incorporate one or more other metals, such as Zr, ti, B, la, ce.
The fifth aspect of the invention provides an application of the hydrogenation catalyst in a hydrocarbon-containing material hydrogenation process.
In the above application, the hydrocarbon-containing material is: atmospheric residuum and vacuum residuum, preferably vacuum residuum.
In the above application, the reaction conditions are: the reaction temperature is 400-430 ℃, the reaction pressure is 12-18 MPa, and the volume space velocity is 0.2-0.5 h -1 The volume ratio of hydrogen to oil is 400-800.
Compared with the prior art, the carrier material, the preparation method, the catalyst and the application thereof provided by the invention have the following advantages:
1. in the preparation method of the carrier material, the nucleation raw material is heated to be liquid, the nucleation raw material is pumped into a spray drying device to be changed into small liquid drops, meanwhile, the pumped pseudo-boehmite powder is adsorbed on the surfaces of the small liquid drops and grows gradually, and finally, the small liquid drops become solid after being discharged out of the spray drying device, so that a carrier matrix is obtained. Because the small liquid drops have good cohesiveness, the adsorbed pseudo-boehmite powder has stronger interaction, and the strength of a carrier matrix is improved.
2. In the preparation method of the carrier material, the carrier precursor is treated under the vacuum condition, firstly, the moisture in the carrier mother balls is gradually volatilized under the relatively low temperature state, then the temperature is increased to change the nucleation material into liquid, under the vacuum condition, the nucleation material slowly flows outwards along the carrier pore canal from the center of the carrier, then the carrier is quickly taken out for cooling, and the nucleation material is gradually solidified in the carrier pore canal to change the carrier into a hollow structure.
3. According to the preparation method of the carrier material, the high-molecular polymer solution and the pseudo-boehmite powder are sequentially and alternately added in the process of preparing the carrier precursor by adopting the rolling ball method, the high-molecular polymer solution is firstly adsorbed on the surface of the carrier mother ball to increase the surface cohesiveness of the carrier mother ball, and then the pseudo-boehmite powder is well adhered to the carrier mother ball and is alternately added until the preparation is finished. The high molecular polymer can enhance the cohesiveness between the pseudo-boehmite powder in the drying process, so that the acting force between the pseudo-boehmite powder is stronger, and the prepared hollow alumina carrier has stronger wear resistance; meanwhile, in the roasting process of the carrier precursor, the high molecular polymer is decomposed into gas to be discharged, and the hole expanding effect on the alumina carrier is also realized.
4. In the preparation method of the carrier material, the nucleation substances are completely combusted in the roasting process of the carrier precursor and become gas to be discharged, so that the alumina with the hollow inner layer is prepared, and the discharged gas plays a role in reaming the alumina, so that the macropore proportion is improved, the catalyst has higher metal capacity, the stability of the catalyst in the long-period running process of the device is ensured, and the preparation method is particularly suitable for the heavy oil and residual oil hydrogenation field.
5. In the catalyst preparation method provided by the invention, the prepared catalyst is hollow, so that the diffusion path of reactants in the catalyst is shortened, the internal pore canal of the catalyst can be better utilized, and the utilization rate of the catalyst is improved.
Detailed Description
The technical scheme and effect of the present invention are further described below by means of specific examples. In the invention, the weight percent is the mass fraction.
The specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen physical adsorption method, and are specifically measured by adopting a low-temperature nitrogen adsorption instrument of ASAP2420 model of America microphone company; the specific process comprises the following steps: and (3) taking a small amount of samples, carrying out vacuum treatment for 3-4 hours at 300 ℃, and finally, placing the products under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen adsorption-desorption test. Wherein the surface area is obtained according to the BET equation and the pore size distribution is obtained according to the BJH model.
The method for measuring the water absorption of the carrier comprises the following steps: the support (by weight) was immersed in water (by volume) for 2 hours, the ratio of support (by weight g) to water (by volume ml) being 1:3, separating the water-absorbed carrier from the water, and calculating the water absorption volume of the carrier, wherein the water absorption rate of the carrier is=the water absorption volume of the carrier/the weight of the carrier.
The abrasion of the spherical carrier is tested by adopting a high-speed air jet method. The method has been formulated by the United states ASTM as a small particle catalyst attrition performance test standard, see ASTM D5757-00 (Standard Test Method for Determination of Attrition and Abrasion of Powdered Catalysts by Air Jets). The basic principle is that under the action of high-speed airflow, catalyst particles are in a fluidized state, fine powder is generated by friction among the particles and between the particles and the wall, and the amount of the fine powder generated in unit time of unit mass of the catalyst, namely the attrition index (attrition), is used as an index for evaluating the attrition resistance of the catalyst.
Example 1
(1) Carrier preparation
Heating 500g vacuum residue with initial boiling point greater than 450deg.C to 120deg.C, spraying downwards through a first feed inlet 0.3mm nozzle in spray drying equipment to form mist droplets with diameter of about 0.4mm, and roasting 600g pseudo-boehmite powder (600 deg.C, dry 70% and specific surface 320 m) with nitrogen gas at 60deg.C from a second feed inlet 2 And/g, pore volume of 0.95 mL/g) is sprayed upwards, the nucleation material sprayed from the first feed inlet is in reverse contact with pseudo-boehmite powder entering from the second feed inlet, and after the treated material is discharged from the bottom of the spray drying equipment, the treated material is further cooled for 2 hours at 30 ℃ to obtain carrier mother balls with the particle size of 0.4-0.5 mm.
100g of carrier mother pellets are placed in a ball rolling machine, 3360mL of aqueous solution containing 88.2g of starch and 4200g of pseudo-boehmite powder (measured at 600 ℃ on a dry basis) are alternately sprayed in turn in the rolling process, the rotational speed of the ball rolling machine is 35 rpm, and after the ball forming is finished, a carrier precursor is obtained. And (3) vacuum drying the carrier precursor for 4 hours at 70 ℃, wherein the relative vacuum degree is-0.1 MPa, then heating to 100 ℃, treating for 10 minutes, taking out the material, roasting for 1 hour at 300 ℃ and 3 hours at 700 ℃ in a nitrogen atmosphere, and obtaining the hollow carbon-containing spherical alumina carrier with the carbon content of 4.4% and the diameter of the inner hollow part of 0.3-0.4 mm. The carrier properties are listed in table 1.
(2) Catalyst preparation
2.79g of phosphoric acid H 3 PO 4 (concentration is 85 wt%) is dissolved in 100mL of water, then 6.06g of molybdenum trioxide and 2.78g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and after filtration, the constant volume is 150mL, thus obtaining the Mo-Ni-P water solution.
Adding the Mo-Ni-P water solution into 90.8g of prepared carrier, mixing uniformly, standing for 3h, stirring at 70 ℃ until the solution is evaporated to dryness, drying the obtained sample at 110 ℃ for 4h, and roasting at 450 ℃ for 3h in air atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 6.0wt%, the content of NiO is 1.5wt%, and P is 2 O 5 The content was 1.7wt%. The attrition data of the catalyst are shown in table 2.
(3) Catalyst evaluation
The activity of the catalyst was evaluated by autoclave, and the properties of the raw oil used are shown in Table 3, and the evaluation conditions are: the reaction pressure is 15.0MPa, the reaction temperature is 430 ℃, the reaction time is 1h, the oil ratio is 13:1, and the evaluation results are shown in Table 4.
Example 2
(1) Carrier preparation
Heating 500g vacuum residue with initial boiling point greater than 450deg.C to 120deg.C, spraying downwards through a first feed inlet 0.4mm nozzle in spray drying equipment to form mist droplets with diameter of about 0.5mm, and roasting 800g pseudo-boehmite powder (600 deg.C, dry 70% and specific surface 320 m) with nitrogen gas at 60deg.C from a second feed inlet 2 Per gram, pore volume 0.95 mL/g) is sprayed upwards, and the nucleation material sprayed from the first feeding port and the second feeding port are fedThe added pseudo-boehmite powder is reversely contacted, the treated material is discharged from the bottom of the spray drying equipment and is further cooled for 2 hours at 30 ℃ to obtain the carrier mother balls with the particle size of 0.5-0.6 mm.
100g of carrier mother balls are placed into a ball rolling machine, 4000mL of aqueous solution containing 210g of starch and 5000g of pseudo-boehmite powder (measured at 600 ℃ on a dry basis) are alternately sprayed in turn in the rolling process, the rotating speed of the ball rolling machine is 35 r/min, and after the ball forming is finished, a carrier precursor is obtained. And (3) vacuum drying the carrier precursor for 4 hours at 70 ℃, wherein the relative vacuum degree is-0.1 MPa, then heating to 100 ℃, treating for 10 minutes, taking out the material, roasting for 1 hour at 300 ℃ and 3 hours at 700 ℃ in a nitrogen atmosphere, and obtaining the hollow carbon-containing spherical alumina carrier with the 1.3-1.5 mm, wherein the carbon content is 5.2%, and the diameter of the inner hollow part is 0.4-0.5 mm. The carrier properties are listed in table 1.
(2) Catalyst preparation
5.58g of phosphoric acid H 3 PO 4 (concentration is 85. 85 wt%) is dissolved in 100mL of water, then 12.12g of molybdenum trioxide and 5.56g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and after filtration, the constant volume is 150mL, thus obtaining the Mo-Ni-P water solution.
Adding the Mo-Ni-P water solution into 81.6g of prepared carrier, mixing uniformly, standing for 3h, stirring at 70 ℃ until the solution is evaporated to dryness, drying the obtained sample at 110 ℃ for 4h, and roasting at 450 ℃ for 3h in air atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 12.0wt%, the content of NiO is 3.0wt%, and P is 2 O 5 The content was 3.4wt%. The attrition data of the catalyst are shown in table 2.
(3) Catalyst evaluation
The catalyst was evaluated at 425℃and the results of the evaluation are shown in Table 4, except that the catalyst was used in the same manner as in example 1.
Example 3
(1) Carrier preparation
Heating 500g vacuum residue with initial boiling point greater than 450deg.C to 120deg.C, spraying downwards through a first feed inlet 0.7mm nozzle in spray drying equipment to form mist droplets with diameter of about 0.7mm, and passing 800g pseudo-boehmite powder (600deg.C) through nitrogen gas with temperature of 60deg.C from a second feed inletRoasting, dry basis 70%, specific surface 320m 2 And/g, pore volume of 0.95 mL/g) is sprayed upwards, the nucleation material sprayed from the first feed inlet is in reverse contact with pseudo-boehmite powder entering from the second feed inlet, and after the treated material is discharged from the bottom of the spray drying equipment, the treated material is further cooled for 2 hours at 30 ℃ to obtain carrier mother balls with the particle size of 0.7-0.8 mm.
100g of carrier mother balls are placed into a ball rolling machine, 2400mL of aqueous solution containing 189g of starch and 3000g of pseudo-boehmite powder (dry basis 70%, measured at 600 ℃) are sequentially and alternately sprayed in a rolling process, the rotating speed of the ball rolling machine is 35 rpm, and after the ball forming is finished, a carrier precursor is obtained. And (3) vacuum drying the carrier precursor for 4 hours at 70 ℃, wherein the relative vacuum degree is-0.1 MPa, then heating to 100 ℃, treating for 10 minutes, taking out the material, roasting for 1 hour at 300 ℃ and 3 hours at 700 ℃ in a nitrogen atmosphere, and obtaining the hollow carbon-containing spherical alumina carrier with the carbon content of 8.3% and the diameter of the inner hollow part of 0.6-0.7 mm. The carrier properties are listed in table 1.
(2) Catalyst preparation
8.37g of phosphoric acid H 3 PO 4 (concentration is 85. 85 wt%) is dissolved in 100mL of water, 18.18g of molybdenum trioxide and 8.34g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and after filtration, the constant volume is 150mL, thus obtaining the Mo-Ni-P water solution.
Adding the Mo-Ni-P water solution into 72.4g of prepared carrier, mixing uniformly, standing for 3h, stirring at 70 ℃ until the solution is evaporated to dryness, drying the obtained sample at 110 ℃ for 4h, and roasting at 450 ℃ for 3h in air atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 18.0wt%, the content of NiO is 4.5wt%, and P is the same as that of the catalyst 2 O 5 The content was 5.1wt%. The attrition data of the catalyst are shown in table 2.
(3) Catalyst evaluation
The catalyst was evaluated at a reaction temperature of 420℃and the results of the evaluation are shown in Table 4, except that the catalyst was used in the same manner as in example 1.
Example 4
In example 1, a catalyst was prepared in the same manner as in example 1 except that 12.12g of molybdenum trioxide, 5.56g of basic nickel carbonate and 5.58g of phosphoric acid were used, wherein MoO 3 The content is as follows12.0wt%, niO content 3.0wt%, P 2 O 5 The content was 3.4wt%. The attrition data of the catalyst are shown in table 2.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Example 5
In example 1, a catalyst was prepared in the same manner as in example 1 except that 18.18g of molybdenum trioxide, 8.34g of basic nickel carbonate and 8.37g of phosphoric acid were used, wherein MoO 3 The content of NiO is 18.0wt%, the content of NiO is 4.5wt%, and P is the same as that of the catalyst 2 O 5 The content was 5.1wt%. The attrition data of the catalyst are shown in table 2.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Example 6
In example 1, a catalyst was prepared in which 2.73g of basic cobalt carbonate was used as basic nickel carbonate, 2.73g of methyl cellulose was used as starch, and the remainder was the same as in example 1, wherein MoO 3 The content is 6.0wt%, the CoO content is 1.5wt%, and P 2 O 5 The content was 1.7wt%. The attrition data of the catalyst are shown in table 2.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Example 7
The catalyst of example 1 was used.
The catalyst is subjected to long-period activity evaluation by adopting a small-scale hydrogenation device, the properties of the used raw oil are shown in Table 3, and the evaluation conditions are as follows: the reaction pressure is 15.0MPa, the reaction temperature is 430 ℃ and the volume space velocity is 0.3h -1 The hydrogen oil volume ratio is 600:1, the running time is 1200h, and the evaluation results are shown in Table 5.
Comparative example 1
(1) Carrier preparation
1000g of pseudo-boehmite powder (70% on a dry basis, measured at 600 ℃) was used as in example 1, and the pellets were formed in a ball mill, and 800mL of an aqueous solution containing 21g of starch was injected during the rolling, and the rotational speed of the ball mill was 35 rpm, after the completion of the pellet forming, a carrier precursor was obtained. And drying the carrier precursor at 60 ℃ for 8 hours, and roasting at 700 ℃ for 3 hours to obtain the 1.0-1.2 mm spherical alumina carrier. The carrier properties are listed in table 1.
(2) Catalyst preparation
2.79g of phosphoric acid H 3 PO 4 (concentration is 85 wt%) is dissolved in 100mL of water, then 6.06g of molybdenum trioxide and 2.78g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and after filtration, the constant volume is 150mL, thus obtaining the Mo-Ni-P water solution.
Adding the Mo-Ni-P water solution into 90.8g of prepared carrier, mixing uniformly, standing for 3h, stirring at 70 ℃ until the solution is evaporated to dryness, drying the obtained sample at 110 ℃ for 4h, and roasting at 450 ℃ for 3h in air atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 6.0wt%, the content of NiO is 1.5wt%, and P is 2 O 5 The content was 1.7wt%.
(3) Catalyst evaluation
The catalyst was evaluated in the same manner as in example 1, and the catalyst was used in the same volume, and the evaluation results are shown in Table 4.
Comparative example 2
The catalyst of comparative example 1 was used as the catalyst.
The catalyst was evaluated in the same manner as in example 7, and the catalyst was used in the same volume, and the evaluation results are shown in Table 5.
TABLE 1 physicochemical Properties of the vector
TABLE 2 attrition of catalyst
TABLE 3 Properties of raw oil
Table 4 results of catalyst evaluation
The results of the evaluation after the comparison with the activity of comparative example are shown in Table 4, with the activity of comparative example 1 being 100. Compared with comparative example 1, the catalyst of example 1 has higher relative demetallization rate and relative desulfurization rate, and the catalyst of example 1 has lower catalyst stack ratio, lower catalyst quality and higher catalyst utilization rate due to the same volume used for the activity evaluation catalyst.
TABLE 5 catalyst Long period evaluation results
The results of the evaluation after the comparison with the activity of comparative example are shown in Table 5, with the activity of comparative example 2 being 100. As can be seen from the long-period evaluation results of the catalysts in Table 5, the catalyst of example 1 has significantly higher relative demetallization rate and relative desulfurization rate than those of comparative example 1, the catalyst volume is the same, the catalyst stack ratio of example 1 is lower, the use amount is smaller, and the catalyst utilization rate is higher.
Claims (22)
1. A method of preparing a carrier material, the method comprising:
(1) Preparing a carrier mother ball: the nucleation material is contacted with pseudo-boehmite powder carried by carrier gas in the form of fog drops for treatment; the nucleation material is a hydrocarbon-containing material, and the initial boiling point of the hydrocarbon-containing material is more than 350 ℃;
(2) Preparing a carrier precursor: the carrier mother ball obtained in the step (1) is contacted with pseudo-boehmite powder and a high-molecular polymer solution for treatment; the high molecular polymer is one or more of starch, sesbania powder and methyl cellulose;
(3) Preparing a carrier: treating the carrier precursor obtained in the step (2) under vacuum condition, and carrying out high-temperature heat treatment under inert atmosphere after the treatment is completed; the vacuum treatment conditions are as follows: the relative vacuum degree is-0.2-0 MPa, and the treatment temperature is 60-120 ℃; the high-temperature heat treatment comprises two sections, wherein the temperature of the first section heat treatment is 200-400 ℃ and the temperature of the second section heat treatment is 500-900 ℃.
2. A method of preparing a support material according to claim 1, characterized in that: the nucleation material in the step (1) is a hydrocarbon-containing material, and the initial distillation point of the hydrocarbon-containing material is more than 450 ℃.
3. A method of preparing a support material according to claim 1, characterized in that: the nucleation material in the step (1) is selected from one or more of atmospheric residuum, vacuum residuum, asphalt and wax oil.
4. A method of preparing a support material according to claim 1, characterized in that: the carrier gas in the step (1) is one or more of nitrogen and inert gas, and the carrier gas is heated to 50-100 ℃.
5. A method of preparing a support material according to claim 1, characterized in that: the treatment in step (1) is accomplished in a spray drying apparatus or spray dipping apparatus.
6. A method of preparing a support material according to claim 1, characterized in that: the treatment process in the step (1) is as follows: firstly, heating a nucleation material to a liquid state, wherein the heating temperature is 100-200 ℃, then spraying into the nucleation material through a spray drying device or a first feed inlet in a spray dipping device to form small fog drops, spraying pseudo-boehmite powder into the nucleation material through a carrier gas from a second feed inlet, and cooling the treated material to obtain a carrier mother ball, wherein the cooling temperature is 20-40 ℃.
7. The method for preparing a carrier material according to claim 6, wherein: the nucleation material sprayed from the first feeding hole is in reverse contact with the pseudo-boehmite powder entering from the second feeding hole.
8. A method of preparing a support material according to claim 1, characterized in that: the particle size of the carrier mother balls is controlled to be 0.2-0.8 mm.
9. A method of preparing a support material according to claim 1, characterized in that: the pseudo-boehmite in the step (1) and the pseudo-boehmite in the step (2) are respectively the same pseudo-boehmite powder or different pseudo-boehmite powders.
10. A method of preparing a support material according to claim 1, characterized in that: in the step (2), the carrier precursor is obtained by uniformly adding the pseudo-boehmite powder and the solution into the carrier mother balls in the rolling process.
11. A method of preparing a support material according to claim 1, characterized in that: the treatment process in the step (2) is to add the carrier mother balls into the high polymer solution and the pseudo-boehmite powder uniformly and alternately in sequence in the rolling process to obtain the carrier precursor.
12. A method of preparing a support material according to claim 1, characterized in that: the high polymer solution in the step (2) is obtained by uniformly mixing a high polymer and water at 40-60 ℃, wherein the high polymer is starch.
13. A method of preparing a support material according to claim 1, characterized in that: the addition amount of the high molecular polymer is 1-10wt% of the weight of the pseudo-boehmite powder in the step (2).
14. A method of preparing a support material according to claim 1, characterized in that: the vacuum treatment conditions in the step (3) are as follows: the relative vacuum degree is-0.1 MPa.
15. A process for the preparation of a support material according to claim 1 or 14, characterized in that: the vacuum treatment in the step (3) comprises two steps of treatment, wherein the treatment temperature in the first step is 60-90 ℃, the treatment time is 3-8 h, the treatment temperature in the second step is 90-120 ℃, and the treatment time is 5-15 min.
16. A method of preparing a support material according to claim 1, characterized in that: the first heat treatment time is 0.5-3 h; the temperature of the second heat treatment is 600-800 ℃; the heat treatment time is 1-5 h.
17. A method of preparing a support material according to claim 1, characterized in that: the inert atmosphere in the step (3) is nitrogen and/or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
18. A method of preparing a support material according to claim 1, characterized in that: the particle size of the carrier in the step (3) is 0.8-2.0 mm.
19. A support material obtainable by the process of any one of claims 1 to 18, said support material being hollow carbonaceous alumina, the specific surface area of the support material being from 180 to 320m 2 Per g, pore volume is 0.60-1.0 mL/g, and water absorption rate is 1.0-1.20 mL/g.
20. A process for preparing a hydrogenation catalyst comprising introducing an active metal component onto a support material according to claim 19, and further drying and calcining to obtain the hydrogenation catalyst.
21. A hydrogenation catalyst obtained by the preparation method of claim 20, wherein the hydrogenation catalyst comprises a hydrogenation active metal component and a carrier, the hydrogenation active metal component is one or more of group VIB metals and/or group VIII metals, and the carrier is hollow carbonaceous alumina.
22. Use of the hydrogenation catalyst of claim 21 in a process for hydrogenating a hydrocarbonaceous feedstock.
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| CN102031139A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Catalytic cracking method for hydrocarbon oil |
| CN103041868A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of spherical catalyst carrier |
| JP2017196550A (en) * | 2016-04-25 | 2017-11-02 | 日揮触媒化成株式会社 | Hydrogenation treatment catalyst for hydrocarbon oil, method for producing the same, and hydrogenation treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031139A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Catalytic cracking method for hydrocarbon oil |
| CN103041868A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of spherical catalyst carrier |
| JP2017196550A (en) * | 2016-04-25 | 2017-11-02 | 日揮触媒化成株式会社 | Hydrogenation treatment catalyst for hydrocarbon oil, method for producing the same, and hydrogenation treatment method |
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